Abstract The sodium-rich sulfido and selenido metallates Na12MnIn2 Q 10 (Q = S/Se) were synthesized in pure phase from melts composed of stoichiometric quantities of the manganese monochalcogenides MnQ, elemental indium and the chalcogens together with either Na2S (Q = S) or elemental sodium (Q = Se) as starting material. The samples were heated up to maximum temperatures of 1000/900 °C under an argon atmosphere; crystallization was achieved by slow cooling rates of 10 K h−1. The two isotypic compounds (monoclinic, space group P21/m, a = 678.26(2)/698.85(10), b = 2202.77(7)/2298.7(3), c = 766.39(3)/800.59(13) pm, β = 90.232(2)/90.147(5)°, Z = 2, R1 = 0.0516/0.0575) crystallize in a new structure type. According to the division of the formula as Na12[InQ 4][MnInQ 6] the salts contain ortho indate anions [InIII Q 4]5− besides hetero-bimetallic dimers [MnIIInIII Q 6]7−, which consist of two edge-sharing [MQ 4] tetrahedra. The seven crystallographically different sodium cations exhibit an either tetrahedral or octahedral coordination by the chalcogen atoms. Thus, the overall structure of the salt is best described by a hexagonal close packing of the sulfide/selenide anions, in which the octahedral voids of every second interlayer section are fully occupied by the (overall 5/f.u.) Na + positions with CN = 6. In the other half of the interlayer sheets, all tetrahedral voids (overall 10/f.u.) are occupied by the seven CN = 4 Na + cations, one In3+ of the ortho anion and the two Mn2+/In3+ cations (which statistically occupy one crystallographic site). This structure relation is also verified by a Bärnighausen group-subgroup tree connecting the h.c.p. (Mg type) aristotype (with its tetrahedral and octahedral voids) by an overall index of 60 with the structure of the two title compounds.

中文翻译：

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新的富钠混合 Mn/In 硫属元素金属化物 Na12MnIn2Q10 (Q = S, Se)

摘要 富钠的硫化物和硒化物金属盐 Na12MnIn2 Q 10 (Q = S/Se) 是在纯相中由熔融态合成的或元素钠（Q = Se）作为起始原料。在氩气气氛下将样品加热至最高温度 1000/900 °C；结晶是通过 10 K h-1 的缓慢冷却速率实现的。两种同型化合物（单斜，空间群 P21/m，a = 678.26(2)/698.85(10)，b = 2202.77(7)/2298.7(3)，c = 766.39(3)/800.59(13) pm， β = 90.232(2)/90.147(5)°, Z = 2, R1 = 0.0516/0.0575) 以新的结构类型结晶。根据分子式为 Na12[InQ 4][MnInQ 6] 的划分，除了异双金属二聚体 [MnIIInIII Q 6]7- 外，盐还含有原位茚酸根阴离子 [InIII Q 4]5-，由两个共享边缘[MQ 4] 四面体。七个晶体学上不同的钠阳离子通过硫属元素原子表现出四面体或八面体配位。因此，盐的整体结构最好通过硫化物/硒化物阴离子的六边形紧密堆积来描述，其中每第二个夹层部分的八面体空隙被（整体 5/fu）Na + 位置完全占据，CN = 6. 在另一半夹层片中，所有四面体空隙（总共 10/fu）被七个 CN = 4 Na + 阳离子、一个邻位阴离子的 In3+ 和两个 Mn2+/In3+ 阳离子（统计上占一个晶体位点）。